Difluorophenyl derivatives, liquid-crystal compounds, and liquid-crystal composition

ABSTRACT

Disclosed are liquid crystalline compounds which (i) are characterized in that the compounds have a wide temperature range in which the compounds exhibit a liquid crystal phase, are low in viscosity, and have a negative and large Δε, (ii) are readily mixed with other various liquid crystal materials even at low temperatures, and (iii) are useful as component of liquid crystal compositions suitable both for TFT type display mode and IPS mode; and liquid crystal composition comprising the liquid crystalline compound; the compounds are expressed by the general formula (1)                    
     wherein R 1  represents an alkyl group having 1 to 15 carbon atoms; ring A 1 , ring A 2 , and ring A 3  independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom; X 1 , X 2 , and X 3  independently represent —(CH 2 ) 4 —, —(CH 2 ) 3 O—, —O(CH 2 ) 3 —, or single bond; Y 1  represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms; m and n are independently 0 or 1; and any atom which constitutes this compound may be replaced by its isotope.

This application is a 371 application of International Application No. PCT/JP97/04633 filed Dec. 16, 1997.

TECHNICAL FIELD

The present invention relates to liquid crystalline compounds and liquid crystal compositions. More specifically, the invention relates to novel liquid crystalline compounds simultaneously having butylene group or propylenoxy group, and 2,3-difluorophenyl group in the compounds; to liquid crystal compositions comprising the compound; and further to liquid crystal display devices fabricated by using the liquid crystal composition.

BACKGROUND ART

Display devices produced by employing optical anisotropy and dielectric anisotropy which are characteristics of liquid crystalline compounds (the term “liquid crystalline compounds” is used in this specification as a general term for the compounds which exhibit a liquid crystal phase and for the compounds which do not exhibit a liquid crystal phase but are useful as component of liquid crystal compositions) have widely been utilized for tabletop calculators, word processors, and TV sets including watches, and the demand for the devices are rising year after year.

Liquid crystal phase is broadly classified into nematic phase, smectic phase, and cholesteric phase. Among them, nematic phase has most widely been employed for display devices. As display mode applied for liquid crystal display, TN (twisted nematic) display mode, DS (dynamic scattering) display mode, guest-host display mode, and DAP (Deformation of Aligned Phases) display mode have been developed corresponding to electro-optic effects.

In recent years, coloring of liquid crystal displays has rapidly been advanced, and thin film transistor (TFT) display mode and super twisted nematic (STN) display mode are main streams in TN display mode as display mode. On the other hand, CRT which is a main stream of current television screen is expected to be replaced by liquid crystal displays sooner or later. In order to realize the replacement, liquid crystal displays must have display characteristics comparable to those of CRT.

In the research and development of liquid crystal displays, one's energies have been devoted to the improvement of response speed, contrast, and viewing angle as important subject. Among them, response speed and contrast became such an extent as equal to those of CRT as a result of repeated improvements in TFT display mode. However, a wide viewing angle comparable to that of CRT has not yet been actualized, whereas some improvements such as an improvement in the orientational direction of liquid crystal molecules and the use of a phase difference plate have been made as to viewing angle.

Although it is an active matrix mode similar to that of TFT display mode, in-plane-switching (IPS) display mode which is characterized in that comb type electrodes are formed only one side of substrate is lately performed on the stage as a mode for actualizing a wide viewing angle (G. Baur, Freiburger Arbeistagung Flussigkristalle, Abstract No. 22 (1993) and M. Oh-e et al., ASIA DISPLAY '95, 577 (1995)). When liquid crystalline compounds having a negative dielectric anisotropy value (Δε) was used in IPS display mode, a dramatically wide viewing angle was obtained.

However, this IPS display mode has such a defect that response speed is considerably low compared with conventional TFT display mode or STN display mode. Then, liquid crystalline compounds having a negative and large Δε and a low viscosity have been required in IPS display mode.

Also, since active matrix driving mode is employed in IPS mode as described above, liquid crystalline compounds having a high voltage holding ratio (V. H. R.) are more preferable.

Various compounds having a negative dielectric anisotropy value are already known. In Laid-open Japanese Patent Publication No. Hei 2-4724 and Tokuhyo (Laid-open Japanese WO publication) No. Hei 2-503441, compounds having 2,3-difluoro-1,4-phenylene group in their partial structure are disclosed as liquid crystal compound having a negative Δε.

It is considered that in the compounds having such partial structure, fluorine atoms substituted at positions 2 and 3 act so as to increase dipole moment in the direction of the minor axis of molecules to make dipole moment of the major axis smaller than the dipole moment in the direction of minor axis, and as the result, the compounds come to have a negative dielectric anisotropy value. However, compounds having such partial structure become slightly narrow in their temperature range exhibiting a liquid crystal phase compared with compounds in which hydrogen atoms of phenylene group are not replaced by fluorine atoms, their miscibility with other liquid crystalline compounds particularly at very low temperatures can hardly be said to be excellent, and sometimes such phenomena that smectic phase is developed and crystals are separated in liquid crystal compositions in a low temperature region are observed.

Compounds expressed by the following formula (a) are described in Tokuhyo No. Hei 2-503441:

wherein R and R′ represent an alkyl group and alkoxy group, respectively.

Whereas structural formula of the compounds is described in the publication mentioned above, physical properties and the likes necessary for judging the utility of the compounds as liquid crystalline compound are not described at all therein. Based on the consideration by the present inventors, whereas an improvement in miscibility by the compounds of the formula (a) described above compared with compounds having no 1,2-ethylene group can be surmised since the compounds of the formula (a) have 1,2-ethylene group as bonding group in skeleton structure, their effect can not be said to be sufficient.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide liquid crystalline compounds which are wide particularly in temperature range of liquid crystal phase, have a low viscosity, have a negative and large Δε, and are improved in solubility at low temperatures; to provide liquid crystal compositions comprising the compound; and to provide liquid crystal display devices fabricated by using the liquid crystal composition, thereby to overcome the problems in conventional technologies described above.

Then, compounds expressed by the general formula (1) and simultaneously having butylene group or propylenoxy group, and 2,3-difluoro-1,4-phenylene group in the structure of compounds were diligently investigated by the present inventors. As the result of the investigation, it has been found out that the compounds are characterized in that they are wide in temperature range exhibiting a liquid crystal phase, are low in viscosity, and have a negative and large Δ∈, as well as they are remarkably excellent in miscibility at low temperatures, leading to the accomplishment of the present invention.

That is, the present invention is summarized as follows:

[1] A liquid crystalline compound expressed by the general formula (1)

 wherein R¹ represents an alkyl group having 1 to 15 carbon atoms in which alkyl group, not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom; X¹, X², and X³ independently represent —(CH₂)₄—, —(CH₂)₃O—, —O(CH₂)₃—, or single bond; Y¹ represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1; and any atom which constitutes this compound may be replaced by its isotope.

[2] The liquid crystalline compound recited in paragraph [1] above wherein ring A¹ represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X¹ represents —(CH₂)₄— or —(CH₂)₃O—; and either m and n are 0 in the general formula (1).

[3] The liquid crystalline compound recited in paragraph [1] above wherein ring A¹and ring A² independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X¹ represents —(CH₂)₄— or —(CH₂)₃O—; X² represents single bond; and m is 1 and n is 0 in the general formula (1).

[4] The liquid crystalline compound recited in paragraph [1] above wherein ring A¹ and ring A² independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X² represents —(CH₂)₄— or —(CH₂)₃O—; X¹ represents single bond; and m is 1 and n is 0 in the general formula (1).

[5] The liquid crystalline compound recited in paragraph [1] above wherein ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X¹ represent —(CH₂)₄— or —(CH₂)₃O—; either X² and X³ represent single bond; and m is 1 and n is 1 in the general formula (1).

[6] The liquid crystalline compound recited in paragraph [1] above wherein ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X² represents —(CH₂)₄— or —(CH₂)₃O—; either X¹ and X³ represent single bond; and m is 1 and n is 1 in the general formula (1).

[7] The liquid crystalline compound recited in paragraph [1] above wherein ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X³ represents —(CH₂)₄— or —(CH₂)₃O—; either X¹ and X² represent single bond; and m is 1 and n is 1 in the general formula (1).

[8] A liquid crystal composition comprising at least two components and comprising at least one liquid crystalline compound expressed by the general formula (1)

 wherein R¹ represents an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom; X¹, X², and X³ independently represent —(CH₂)₄—, —(CH₂)₃O—, —O(CH₂)₃—, or single bond; Y¹ represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1; and any atom which constitutes this compound may be replaced by its isotope.

[9] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4)

 wherein R² represents an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring C represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; and each atom which constitutes those compounds may be replaced by its isotope.

[10] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6)

 wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y³ represents —CN or —C≡C—CN; ring D represents trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring F represents trans-1,4-cyclohexylene group or 1,4-phenylene group; Z³ represents 1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom; a, b, and c are independently 0 or 1; and each atom which constitutes those compounds may be replaced by its isotope.

[11] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

 wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one hydrogen atom may be replaced by fluorine atom; Z⁴ and Z⁵ independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡C—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.

[12] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12)

 wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring K and ring M independently represent trans-1,4-cyclohexylene or 1,4-phenylene; L⁶ and L⁷ independently represent hydrogen atom or fluorine atom, but in no case simultaneously represent L⁶ and L⁷ hydrogen atom; Z⁶ and Z⁷ independently represent —CH₂CH₂—, —COO—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.

[13] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12) described above.

[14] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

[15] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6) described above, and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

[16] A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound recited in any one of paragraphs [1] to [7] above, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4) described above, comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6) described above, and comprising, as a fourth component, at least one component selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9) described above.

[17] A liquid crystal composition comprising at least one optically active compound in addition to the liquid crystal composition recited in any one of paragraphs [8] to [16] above.

[18] A liquid crystal display device fabricated by using the liquid crystal composition recited in any one of paragraphs [8] to [17] above.

Liquid crystalline compounds of the present invention expressed by the general formula (1) are two to four rings compounds having butylene group or propylenoxy group, and 2,3-difluorophenyl group at the same time in the molecular structure. As a matter of course, these liquid crystalline compounds are extremely stable physically and chemically under the environment in which liquid crystal display devices are used, and the compounds are characterized in that they are wide in temperature range exhibiting a liquid crystal phase, excellent in solubility in liquid crystal compositions even at low temperatures, and low in viscosity, and have a negative and large Δε.

As described in the section of BACKGROUND ART, whereas compounds having 2,3-difluoro-1,4-phenylene group as a partial structure are already disclosed in patent publications, it is a fact discovered for the first time by the present inventors that the compounds simultaneously having 1,4-butylene group or propylenoxy group as bonding group and 2,3-difluoro-1,4-phenylene group exhibit the characteristic described above, and it is difficult to expect such fact from conventional technology.

In the compounds of the present invention, it is possible to optionally adjust desired physical properties by selecting a proper ring structure, bonding group, and lateral structure among molecule constituting elements. Accordingly, novel liquid crystal compositions and liquid crystal display devices having excellent characteristics, specifically

1) having a wide temperature range of liquid crystal phase,

2) being low in viscosity, and having a negative and large Δε,

3) separating no crystals and developing no smectic phase even at very low temperatures,

4) being physically and chemically stable, and being possible to expand the temperature range of their usage, to drive at a low voltage, and to realize a high speed response and high contrast can be provided by using the compound of the present invention as component of liquid crystal compositions.

While any of the compounds of the present invention exhibits preferable physical properties, liquid crystal compositions having physical properties suitable for their use can be produced by using the compound which is expressed by the general formula (1) in which ring A¹, ring A², ring A³, X¹, X², X³, m, and n are properly selected.

That is, when compounds having a negative and large Δε are necessary, it is sufficient to suitably select 2,3-difluoro-1,4-phenylene group for any one of ring A¹, ring A², ring A³, and when compounds having a high optical anisotropy value are necessary, it is sufficient to select compounds in which any one of ring A¹, ring A², and ring A³ is 1,4-phenylene group, and every one of X¹, X², and X³ is single bond. When compounds having their temperature range of liquid crystal phase at high temperature side are necessary, it is sufficient to suitably select three rings or four rings compounds, and when compounds having their temperature range of liquid crystal phase at low temperature side are necessary, it is sufficient to suitably select two rings compounds, respectively.

Compounds in which hydrogen atom on 1,4-phenylene group is replaced by fluorine atom exhibit an excellent solubility at low temperatures.

Compounds expressed by one of the following general formulas (1-1) to (1-12) can be mentioned as particularly preferable ones among the compounds expressed by the general formula (1):

wherein R¹, ring A¹, ring A², ring A³, and Y¹ have the same meaning as described above.

In the compounds described above, while R¹ represents an alkoxy group, alkoxyalkyl group, alkenyl group, alkenyloxy group, alkenyloxyalkyl group, or alkyloxyalkenyl group having 1 to 15 carbon atoms, particularly preferable groups among them are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, propoxypropyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy, 4-pentynyloxy, methoxy-1-propenyl, methoxy-1-pentenyl, and methoxy-3-pentenyl.

In the compounds described above, while Y¹ represents hydrogen atom, an alkyl group, alkoxy group, alkoxyalkyl group, alkenyl group, alkenyloxy group, alkenyloxyalkyl group, or alkyloxyalkenyl group having 1 to 15 carbon atoms, particularly preferable groups among them are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl, and propoxypropyl.

Liquid crystal compositions of the present invention are described below. Liquid crystal compositions of the present invention preferably comprise at least one compound expressed by the general formula (1) in the ratio of 0.1 to 99.9% by weight to develop excellent characteristics.

More preferably, the liquid crystal compositions provided by the present invention are completed by mixing compounds selected from the group consisting of the compounds expressed by one of the general formulas (2) to (12) depending on the purposes of the liquid crystal compositions in addition to the first component comprising at least one compound expressed by the general formula (1).

The present invention recited in the paragraphs [12] and [13] above are concerned with N type (having a negative Δε) liquid crystal compositions. In the same way as P type (having a positive Δε) liquid crystal compositions, N type liquid crystal compositions can be driven by various driving modes, for example, by IPS mode (In Plane Switching Mode). The present invention recited in paragraphs [9], [10], [11], [14], [15], and [16] are concerned with P type liquid crystal compositions. It is possible to control elastic constants of liquid crystal compositions and to improve the miscibility of the compositions at low temperatures by adding a N type liquid crystalline compound to P type liquid crystal compositions.

Following compounds can preferably be mentioned as ones used in the liquid crystal compositions of the present invention and expressed by one of the general formulas (2) to (4):

wherein R² and Y² have the same meaning as described above.

Compounds expressed by one of the general formulas (2) to (4) have a positive dielectric anisotropy value, are remarkably excellent in thermal stability and chemical stability, and are useful when liquid crystal compositions for TFT (AM-LCD) display mode of which a high reliability such as a particularly high voltage holding ratio or large specific resistivity is required are produced.

When the liquid crystal compositions for TFT display mode are produced, the compounds expressed by one of the general formulas (2) to (4) can be used in the range of 0.1 to 99.9% by weight based on the total amount of liquid crystal composition, and the amount is preferably 10 to 97% by weight and more desirably 40 to 95% by weight. Also, the compositions may further comprise the compound expressed by one of the general formulas (7) to (9) for the purpose of adjusting viscosity. Even when liquid crystal compositions for STN display mode or TN display mode are produced, the compound expressed by one of the general formulas (2) to (4) can be used. In this case, the amount of the compound to be used is preferably less than 50% by weight.

As the compound used in the liquid crystal compositions of the present invention expressed by the general formula (5) or (6), the following compounds can preferably be mentioned:

wherein R³, R⁴, and Y³ have the same meaning as described above.

Compounds expressed by the general formula (5) or (6) have a positive and large dielectric anisotropy value, and are used particularly for the purpose of lowering threshold voltage of liquid crystal compositions. Also, they are used for the purpose of adjusting optical anisotropy value, and widening nematic range such as raising clearing point. Further, they are used even for the purpose of improving the steepness of V-T curve of liquid crystal compositions for STN display mode or TN display mode.

Compounds expressed by the general formula (5) or (6) are useful when liquid crystal compositions particularly for STN display mode or TN display mode are produced.

When the content of the compound expressed by the general formula (5) or (6) in liquid crystal compositions is increased, threshold voltage of liquid crystal compositions lowers but viscosity increases. Accordingly, it is advantageous to use the compound in a large amount since driving at a low voltage becomes possible, so far as viscosity of liquid crystal compositions satisfies required characteristics.

When liquid crystal compositions for STN display mode or TN display mode are produced, the amount of the compound expressed by the general formula (5) or (6) to be used is in the range of 0.1 to 99.9% by weight, preferably 10 to 97% by weight, and more desirably 40 to 95% by weight.

As the compounds used in the liquid crystal compositions of the present invention and expressed by one of the general formulas (7) to (9), the following compounds can preferably be mentioned.

wherein R⁵ and R⁶ have the same meaning as described above.

Compounds expressed by one of the general formulas (7) to (9) have a small absolute value of dielectric anisotropy, and are close to neutral. Compounds expressed by the general formula (7) are used principally for the purpose of adjusting viscosity and adjusting optical anisotropy value of liquid crystal compositions. Compounds expressed by the general formula (8) or (9) are used for the purpose of widening nematic range such as raising clearing point, or for the purpose of adjusting optical anisotropy value.

When the content of the compound expressed by one of the general formulas (7) to (9) in liquid crystal compositions is increased, threshold voltage of liquid crystal compositions rises but viscosity reduces. Accordingly, it is desirable to use the compound in a large amount so far as threshold voltage of liquid crystal compositions satisfies required characteristics. When liquid crystal compositions for TFT are produced, the amount of the compound expressed by one of the general formulas (7) to (9) to be used is preferably less than 40% by weight and more desirably less than 35% by weight. When liquid crystal compositions for STN display mode or TN display mode are produced, the amount is preferably less than 70% by weight and more desirably less than 60% by weight.

As the compounds used in the liquid crystal compositions of the present invention and expressed by one of the general formulas (10) to (12), the following compounds can preferably be mentioned:

wherein R⁷ and R⁸ have the same meaning as described above.

Compounds expressed by one of the general formulas (10) to (12) have a negative dielectric anisotropy value. Compounds expressed by the general formula (10) are two rings compounds, and are used principally for the purpose of adjusting threshold voltage, adjusting viscosity, or adjusting optical anisotropy value. Compounds expressed by the general formula (11) are used for the purpose of widening nematic range such as raising clearing point, or for the purpose of adjusting optical anisotropy value. Compounds expressed by the general formula (12) are used for the purpose of widening nematic range as well as for the purpose of lowering threshold voltage and for the purpose of increasing optical anisotropy value.

Compounds expressed by one of the general formulas (10) to (12) are used principally for N type (having a negative dielectric anisotropy Δε) liquid crystal compositions. When the amount of the compound to be used is increased, threshold voltage of liquid crystal compositions lowers but viscosity increases. Accordingly, it is desirable to use the compound in a small amount so far as threshold voltage of liquid crystal compositions is satisfied. However, since these compounds have an absolute value of dielectric anisotropy value of lower than 5, when the amount of the compound used is less than 40% by weight, driving at a low voltage sometimes becomes impossible.

The amount of the compound expressed by one of the general formulas (10) to (12) to be used in liquid crystal compositions is preferably more than 40% by weight when liquid crystal compositions for N type TFT are produced and the amount is more desirably 50 to 95% by weight.

Further, for the purpose of control the elastic constants of liquid crystal compositions and regulating voltage-transmittance curve (V-T curve), the compound expressed by one of the general formulas (10) to (12) is sometimes added to P type (having positive dielectric anisotropy Δε) liquid crystal compositions. In such case, the amount of the compound expressed by one of the general formulas (10) to (12) to be used in liquid crystal compositions is preferably less than 30% by weight.

With the exception of such specific cases as liquid crystal compositions for OCB (optically Compensated Birefringence) mode and the likes, an optically active compound is usually added to the liquid crystal compositions of the present invention for the purpose of inducing helical structure of liquid crystal composition to adjust required twist angle and to prevent reverse twist. While any known optically active compounds used for such purposes can be added in the liquid crystal compositions of the present invention, the following optically active compounds can be mentioned as preferable examples:

These optically active compounds are usually added to liquid crystal compositions of the present invention to adjust their pitch of twist. The twist pitch is preferably adjusted in the range of 40 to 200 μm in the case of liquid crystal compositions for TFT or TN, and preferably adjusted in the range of 6 to 20 μm in the case of liquid crystal compositions for STN. In the case for bistable TN mode, it is preferable to adjust the pitch in the range of 1.5 to 4 μm. Further, two or more kind of optically active compounds may be added for the purpose of adjusting the dependency of the pitch length on temperature.

Liquid crystal compositions of the present invention can be produced by methods which are conventional by themselves. Generally, a method in which various components are dissolved one another at a high temperature has been adopted.

Further, the liquid crystal compositions of the present invention can be used as ones for guest-host (GH) mode by adding a dichroic dye such as merocyanine type, styryl type, azo type, azomethine type, azoxy type, quinophthalone type, anthraquinone type, and tetrazine type thereto. Alternatively, the liquid crystal compositions can be used as NCAP which is prepared by the microencapsulation of a nematic liquid crystal, or as liquid crystal compositions for polymer dispersed liquid crystal display devices (PDLCD) represented by polymer net work liquid crystal display devices (PNLCD) prepared by forming a polymer of three-dimensional reticulated structure in a liquid crystal. Still further, the liquid crystal compositions of the present invention can be used as ones for electrically controlled birefringence (ECB) mode or dynamic scattering (DS) mode.

[Methods for Producing Compounds]

Compounds of the present invention expressed by the general formula (1) can readily be produced by using ordinary chemical procedures of organic synthesis. For instance, the compounds can readily be synthesized by selecting proper known reactions described in reference books such as Organic Synthesis, Organic Reactions, and Shin-Jikken Kagaku Kouza (Course of New Chemical Experiment), and magazines, and using the reactions in combination.

When butylene group is introduced at the position of a bonding group (X¹, X², and X³), the compounds can be produced, for instance, by the following reaction paths.

In the following, MSG1 and MSG2 independently represent a mesogen (a residue of organic compounds); Hal represents Cl, Br, or I; ring A represents trans-1,4-cyclohexylene group, 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a halogen atom, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group; and Y¹ have the same meaning as described above.

That is, 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium halide (12) and aldehyde derivative (11) are subjected to the Wittig reaction in an ether type solvent such as tetrahydrofuran (hereinafter abbreviated to THF) and diethyl ether in the presence of a base such as sodium methylate, potassium-t-butoxide (t-BuOK), and butyl lithium to obtain compound (13). Subsequently, aldehyde derivative (14) can be obtained by subjecting compound (13) to hydrogen reduction in a mixed solvent of toluene/Solmix in the presence of a metal catalyst such as palladium/carbon and Raney nickel, and then reacting with a mineral acid such as hydrochloric acid and sulfuric acid, or an organic acid such as formic acid and p-toluenesulfonic acid.

Further, in the same way as that wherein compound (13) is obtained from compound (11), compound (16) can be obtained by subjecting compound (14) and compound (15) to the wittig reaction, and aldehyde derivative (17) can be produced by reacting it with the same acid as described above. Subsequently, derivative (19) having butylene group can be produced by reacting Grignard reagent (18) with compound (17) to conduct Grignard reaction, reacting it with the same acid as described above to dehydrate, and further subjecting to hydrogen reduction by using the same metal catalyst as described above.

When propylenoxy group having ether bond is introduced at the position of a bonding group (X¹, X², and X³), the compounds can be produced, for instance, by the following reaction paths.

Aldehyde derivative (14) is reacted with lithium aluminum hydride in a solvent such as toluene, THF, and diethyl ether to reduce thereby to obtain alcohol derivative (20). This alcohol derivative (20) is reacted with hydrobromic acid to produce compound (21). Compound (23) having ether bond can be produced by reacting compound (21) with compound (22) in the presence of sodium hydride.

When 2,3-difluoro-1,4-phenylene group is introduced to a ring structure portion, the compounds can be produced, for instance, by the following reaction paths.

a) The case wherein the introduction portion is located at position 4 relative to MSG1 of benzene derivative:

Compound (25) can be obtained by reacting difluorobenzene derivative (24) with n-butyl lithium or sec-butyl lithium in an ether type solvent such as THF and diethyl ether, reacting with zinc chloride, and then reacting with 2,3-difluoro-1-bromobenzene in the presence of a metal catalyst of palladium (0).

b) The case wherein it is introduced in cyclohexanone derivative having MSG1 at position 4:

Compound (28) can be produced by reacting compound (26) with Grignard reagent (27) to conduct the Grignard reaction, dehydrating by the same procedure as described above, and then subjecting to hydrogen reduction.

Compounds in which ring A¹, ring A², and ring A³ are silacyclohexane rings can be produced according to the method disclosed in Laid-open Japanese Patent Publication No. Hei 7-70148, Laid-open Japanese Patent Publication No. 7-112990, and Laid-open Japanese Patent Publication Nol Hei 7-149770.

Compounds of the present invention expressed by the general formula (1) can be produced by selecting and using proper reactions described above.

Any of the liquid crystalline compounds of the present invention expressed by the general formula (1) thus obtained has such characteristics that the temperature range in which the compound exhibits a liquid crystal phase is wide, viscosity is low, and Δε is negative and large, and the compound is readily mixed with other various liquid crystal materials even at low temperatures. Accordingly, the compound is remarkably excellent as constituent of nematic liquid crystal compositions suitable for TFT type display mode and IPS mode.

BEST MODE FOR CARRYING OUT THE INVENTION

Now, the present invention will be described in more detail with reference to Examples. However, it should be understood that the scope of the present invention is by no means restricted by such specific Examples. In the Examples, the structure of compounds was confirmed by nuclear magnetic resonance spectrum (hereinafter abbreviated to ¹H-NMR) and mass spectrum (hereinafter abbreviated to MS). In the data of ¹H-NMR in the Examples, t indicates triplet, q: quartet, M: multiplet, and J: coupling constant. In the data of MS, M⁺ indicates molecular ion peak. Further, C indicates crystal, S_(A): smectic phase A, S_(B): smectic phase B, N: nematic phase, and Iso: isotropic liquid phase, and the unit of every phase transition temperature is °C.

EXAMPLE 1

Preparation of 2,3-difluoro-1-propyl-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene [Compound expressed by the general formula (1) wherein R¹ is pentyl group, ring A¹ and ring A² are trans-1,4-cyclohexylene group, X¹ is butylene group, X² is single bond, Y¹ is propyl group, m is 1, n is 0 (Compound No. 20)]

First Step

Under nitrogen gas stream, 52.3 g (2150 mmol) of magnesium was added in 100 ml of THF, and a solution of 378 g (1960 mmol) of 2,3-difluoro-1-bromobenzene in 4.0 l of THF was added by drops thereto so that the reaction temperature was maintained at about 50° C. Further, after stirred at room temperature for 1 hour, a solution of 500 g (1630 mmol) of 4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexanone in 5.0 l of THF was added by drops to the solution and stirred at 50 to 60° C. for 2 hours, and then 1.0 l of saturated aqueous ammonium chloride solution was added to the solution to terminate the reaction. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and then it was extracted with 2.0 l of toluene. The organic layer was washed with 1.0 l of water thrice and dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was removed by filtration, 23.7 g of p-toluenesulfonic acid monohydrate was added to the filtrate and heated to reflux for 4 hours. The organic layer was washed with 1.0 l of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 436 g of a crude 1,2-difluoro-3-(4-(4-(trans-4-pentylcyclohexyl)-butyl)cyclohexene-1-yl)benzene.

Second Step

In 4.0 l of mixed solvent of toluene/Solmix (1/1) was dissolved 436 g (1080 mmol) of the crude product obtained by the procedures described above, 21.8 g of 5% by weight-palladium/carbon catalyst was added thereto, and then they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm² for 6 hours. After the catalyst was removed by filtration, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) and recrystallized from heptane twice to obtain 114 g of 1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene.

Third Step

Under nitrogen gas stream, a solution prepared by dissolving 30.0 g (74.1 mmol) of 1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene in 300 ml of THF was cooled down to −70° C., 88.9 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature, and stirred at the same temperature for further 2 hours. Subsequently, a suspension prepared by adding 9.98 g (88.9 mmol) of t-BuOK to 100 ml of THF was added by drops to the reaction liquid while being maintained at the same temperature, and stirred at the same temperature for further 1 hour. To the reaction liquid was added by drops a solution of 15.1 g (88.9 mmol) of propyliodide in 150 ml of THF while being maintained at the same temperature and stirred at the same temperature for 5 hours. The reaction was terminated by adding 200 ml of water to the reaction mixture, and the solvent was distilled off under a reduced pressure. Concentrated residue was extracted with 500 ml of toluene, and the organic layer was washed with 200 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain a crude 2,3-difluoro-1-propyl-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene. This crude product was recrystallized from heptane thrice to obtain 5.40 g (yield 2.82%) of the subject compound.

Phase transition temperature: C 40.2 S_(B) 90.9 N 98.0 Iso; ¹H-NMR: δ: (ppm): 0.50˜2.10 (m, 45H), 2.59 (t, 1H, J=7.3 Hz), 6.70˜7.10 (m, 2H); MS: m/e=446 (M⁺).

EXAMPLE 2

Preparation of 1-ethoxy-2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene [Compound expressed by the general formula (1) wherein R¹ is pentyl group, either ring A¹ and ring A² are trans-1,4-cyclohexylene group, X¹ is butylene group, X² is single bond, Y¹ is ethoxy group, m is 1, and n is 0 (Compound No. 23)]

First Step

Under nitrogen gas stream, a solution of 60.0 g (148 mmol) of 1,2-difluoro-3-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)-cyclohexyl)benzene in 600 ml of THF was cooled down to −70° C., 178 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature, and stirred at the same temperature for 2 hours. Subsequently, a solution of 30.8 g (296 mmol) of trimethyl borate in 300 ml of THF was added by drops thereto while being at the same temperature, and stirred at the same temperature for further 2 hours. After the reaction temperature was gradually raised up to room temperature, 88.9 g (1480 mmol) of acetic acid was added, 134 g (1180 mmol) of 30% hydrogen peroxide was added by drops, and then stirred at room temperature for 3 hours. The reaction was terminated by adding 300 ml of saturated aqueous sodium thiosulfate solution to the reaction mixture, and the solvent was distilled off under a reduced pressure.

Concentrated residue was extracted with 500 ml of toluene and 100 ml of diethyl ether, the organic layer was washed with 150 ml of saturated aqueous sodium thiosulfate solution twice and with 200 ml of water thrice, and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was recrystallized from toluene to obtain 40.0 g of 2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)phenol.

Second Step

In 400 ml of N,N-dimethyl formamide (hereinafter abbreviated to DMF), was dissolved 40.0 g (95.1 mmol) of 2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)phenol, and heated on a water bath up to 50° C. Oily 55% sodium hydride in an amount of 4.97 g (114 mmol) was added thereto, stirred at the same temperature for 10 minutes, and a solution of 15.5 g (142 mmol) of ethyl bromide in 150 ml of DMF was added by drops. After finishing of the dropping, the reaction temperature was raised up to 80° C., and stirred at the same temperature for 5 hours. After cooled down to room temperature, the reaction was terminated by adding 500 ml of water to the reaction mixture, and it was extracted with 1.0 l of toluene. The organic layer was washed with 500 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain a crude 1-ethoxy-2,3-difluoro-4-(trans-4-(4-(trans-4-pentylcyclohexyl)butyl)cyclohexyl)benzene. This crude product was recrystallized from heptane twice and from mixed solvent of heptane/ethanol (6/1) once to obtain 10.3 g (yield 15.5%) of the subject compound.

Phase transition temperature: C 79.2 S_(A) 94.5 N 125.5 Iso; ¹H-NMR: δ: (ppm): 0.50˜2.05 (m, 41H), 2.73 (t, 1H, J=7.3 Hz), 4.09 (q, 2H, J=7.0 Hz), 6.50˜7.00 (m, 2H); MS: m/e=448 (M⁺).

EXAMPLE 3

Preparation of 1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene [Compound expressed by the general formula (1) wherein R¹ is propyl group, either ring A¹ and ring A² are trans-1,4-cyclohexylene group, X¹ is a single bond, X² is butylene group, Y¹ is ethoxy group, m is 1, and n is 0 (Compound No. 94)]

First Step

Under nitrogen gas stream, a mixture of 1330 g (2930 mmol) of 2-(1,3-dioxane-2-yl)ethyltriphenylphosphonium bromide with 6.0 l of THF was cooled down to −30° C., and 303 g (2700 mmol) of t-BuOK was added thereto and stirred for 1 hour. To this mixture was added by drops a solution of 500 g (2250 mmol) of 4-(trans-4-propylcyclohexyl)cyclohexanone in 3.0 l of THF while being maintained at a temperature lower than −30° C. After finishing of the adding, the reaction temperature was gradually raised up to room temperature and they were stirred for further 5 hours. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of toluene/ethyl acetate=9/1) to obtain 652 g of a crude 2-(2-(4-(trans-4-propylcyclohexyl)cyclohexylidene)-ethyl-1,3-dioxane.

Second Step

In 6.5 l of mixed solvent of toluene/Solmix (1/1) was dissolved 652 g (2030 mmol) of the crude product obtained by the procedures described above, 32.6 g of 5% by weight-palladium/carbon catalyst was added thereto, and then they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm² for 6 hours. After the catalyst was removed by filtration, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: toluene) and recrystallized from heptane to obtain 366 g of 2-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)-1,3-dioxane.

Third Step

In 3.0 l of toluene was dissolved 300 g (930 mmol) of the 2-(2-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)ethyl)-1,3-dioxane obtained by the procedures described above, 428 g (9300 mmol) of formic acid was added thereto, and they were heated to reflux for 4 hours. The reaction mixture was washed with 600 ml of saturated aqueous sodium bicarbonate solution twice and with 1.0 l of water five times, and the solvent was distilled off under a reduced pressure to obtain 240 g of a crude 3-(trans-4-(trans-4-propylcyclohexyl)-cyclohexyl)propanal.

Fourth Step

Under nitrogen gas stream, a mixture of 405 g (1180 mmol) of methoxymethyltriphenylphosphonium chloride with 4.0 l of THF was cooled down to −30° C., 122 g (1090 mmol) of t-BuOK was added thereto, and they were stirred for 1 hour. To this mixture was added by drops a solution of 240 g (907 mmol) of the crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propanal in 2.4 l of THF while being maintained at a temperature lower than −30° C. After finishing of the dropping, the reaction temperature was gradually raised up to room temperature, and the mixture was stirred for further 5 hours. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 152 g of a crude 1-methoxy-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butene.

Fifth Step

In 500 ml of toluene was dissolved 50.0 g (171 ml ) of the crude 1-methoxy-4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butene obtained by the procedures in the fourth step, 78.7 g (1710 mmol) of formic acid was added thereto, and then they were heated to reflux for 4 hours. The reaction mixture was washed with 300 ml of saturated aqueous sodium bicarbonate solution twice and with 500 ml of water five times, and the solvent was distilled off under a reduced pressure to obtain 45.1 g of a crude 4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butanal.

Sixth Step

Under nitrogen gas stream, a solution of 30.7 g (194 mmol) of 1-ethoxy-2,3-difluorobenzene in 300 ml of THF was cooled down to −70° C., 194 ml of sec-butyl lithium (1.0M cyclohexane solution) was added by drops thereto while being maintained at the same temperature, and they were stirred at the same temperature for 2 hours. To this reaction mixture was added by drops a solution of 45.1 g (162 mmol) of the crude 4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butanal obtained by the reaction in the fifth step in 450 ml of THF while being maintained at the same temperature, and stirred for 2 hours. Subsequently, they were raised up to −50° C. and stirred for 2 hours. The reaction mixture was added to 200 ml of water to terminate the reaction, the solvent was distilled off under a reduced pressure, the residue was extracted with 500 ml of toluene, and the organic layer was washed with 100 ml of water thrice, and then dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was removed by filtration, 2.83 g of p-toluenesulfonic acid monohydrate was added to the filtrate, and heated to reflux for 4 hours. The organic layer was washed with 200 ml of water thrice and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain 50.2 g of a crude 1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-1-butenyl)benzene.

Seventh Step

In 500 ml of mixed solvent of toluene/Solmix (1/1) was dissolved 50.2 g (120 mmol) of the crude product obtained by the procedures described above, 15.1 g of 5% by weight-palladium/carbon catalyst was added thereto, and they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm² for 6 hours. After the catalyst was removed by filtration, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude 1-ethoxy-2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene. This crude product was recrystallized from heptane twice to obtain 24.3 g (yield 9.90%) of the subject compound.

Phase transition temperature: C 44.4 S_(A) 107.2 N 129.0 Iso; ¹H-NMR: δ: (ppm): 0.45˜2.10 (m, 36H), 2.58 (t, 2H, J=7.0 Hz), 4.09 (q, 2H, J=7.0 Hz), 6.50˜7.00 (m, 2H); MS: m/e=420 (M⁺).

EXAMPLE 4

Preparation of 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluoro-4-(2,3-difluoro-4-pentylphenyl)phenyl ether [Compound expressed by the general formula (1) wherein R¹ is propyl group, either ring A¹ and ring A² are trans-1,4-cyclohexylene group, ring A³ is 2,3-difluoro-1,4-phenylene group, either X¹ and X³ are single bond, X² is propyloxylene group, Y¹ is pentyl group, m is 1, and n is 1 (Compound No. 237)]

First Step

Under nitrogen gas stream, a solution of 400 g (1510 mmol) of the crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propanal obtained in the same manner as in the third step in Example 1 in 2.0 l of THF was added by drops to a mixture which was prepared by adding 43.0 g (1130 mmol) of lithium aluminum hydride to 400 ml of THF cooled down to a temperature lower than 5° C., while being maintained at the same temperature. After finishing of the adding, they were stirred at room temperature for 6 hours. This reaction mixture was gradually added to 500 ml of 2N aqueous sodium hydroxide solution and stirred at 50° C. for 30 minutes. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and the residue was extracted with 2.0 l of ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under a reduced pressure to obtain 341 g of a crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propanol.

Second Step

To 350 ml of xylene were added 341 g (1280 mmol) of the crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propanol obtained by the procedures described above and 881 g (5120 mmol) of 47% hydrobromic acid, water was removed by azeotropic distillation, and then the mixture was stirred at 150° C. for 2 hours. To the reaction mixture was added 1.0 l of toluene, and it was washed with 300 ml of saturated aqueous sodium carbonate solution twice and with 400 ml of water thrice, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 156 g of a crude 1-bromo-3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propane.

Third Step

Under nitrogen gas stream, 29.8 g (683 mmol) of 55% sodium hydride was added to 100 ml of DMF and cooled with water, a solution of 74.0 g (569 mmol) of 2,3-difluorophenol in 700 ml of DMF was added by drops thereto, and they were stirred for 1 hour. To the reaction mixture was added by drops a solution of 156 g (474 mmol) of the crude 1-bromo-3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propane in 400 ml of mixed solvent of DMF/toluene (3/1), and then they were stirred at 80° C. for 3 hours. The reaction mixture was added to 500 ml of water to terminate the reaction, and the organic layer was separated, washed with 500 ml of water thrice, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) and recrystallized from heptane to obtain 101 g of 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluorophenyl ether.

Fourth Step

Under nitrogen gas stream, 101 g (267 mmol) of the 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluorophenyl ether obtained by the procedures described above was dissolved in 1.0 l of THF and cooled down to −70° C. To this solution was added by drops 320 ml of sec-butyl lithium (1.0M, cyclohexane solution) while being maintained at the same temperature, and stirred at the same temperature for 2 hours. To the reaction mixture was added by drops 640 ml of zinc chloride (0.5M, THF solution), and stirred at the same temperature for 1 hour, the reaction temperature was gradually raised up to room temperature, and they were stirred for 1 hour. To the reaction mixture was added 1.00 g of tetrakis(triphenylphosphine)palladium (0), and a solution of 61.8 g (15.9 mmol) of 2,3-difluoro-1-bromobenzene in 600 ml of THF was added by drops thereto, and heated to reflux for 3 hours. The reaction mixture was added to 1.0 l of water to terminate the reaction, the solvent was distilled off under a reduced pressure, and the residue was extracted with 3.0 l of toluene. The organic layer was washed with 1.0 l of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: toluene) to obtain 55.3 g of a crude 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluoro-4-(2,3-difluorophenyl)phenyl ether.

Fifth Step

Under nitrogen gas stream, a solution prepared by dissolving 55.3 g (112 mmol) of the 3-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)propyl 2,3-difluoro-4-(2,3-difluorophenyl)phenyl ether obtained by the procedures described above in 550 ml of THF was cooled down to −70° C., and 134 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature and stirred at the same temperature for 2 hours. To the reaction mixture was added by drops a suspension which was prepared by adding 15.0 g (134 mmol) of t-BuOK to 150 ml of THF, while being maintained at the same temperature, and stirred at the same temperature for further 1 hour. To the reaction mixture was added by drops a solution of 26.5 g (134 mmol) of pentyliodide in 300 ml of THF while being maintained at the same temperature and stirred at the same temperature for 5 hours. The reaction mixture was added to 300 ml of water to terminate the reaction, and the solvent was distilled off under a reduced pressure. The residue was extracted with 700 ml of toluene, and the organic layer was washed with 300 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude 3-(trans-4-(trans-4-propylcyclohexyl)propyl 2,3-difluoro-4-(2,3-difluoro-4-pentylphenyl)phenyl ether. This crude product was recrystallized from heptane twice and from mixed solvent of heptane/ethanol (4/1) once to obtain 10.2 g (yield 1.21%) of the subject compound.

MS: m/e=560 (M⁺).

EXAMPLE 5

Preparation of 1-ethoxy-2,3-difluoro-4-(2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)phenyl)benzene [Compound expressed by the general formula (1) wherein R¹ is propyl group, either ring A¹ and ring A² are trans-1,4-cyclohexylene group, ring A³ is 2,3-difluoro-1,4-phenylene group, either X¹ and X³ are single bond, X² is butylene group, Y¹ is ethoxy group, m is 1, and n is 1 (Compound No. 238)]

First Step

Under nitrogen gas stream, 8.05 g (331 mmol) of magnesium was added to 20.0 ml of THF, and a solution of 58.1 g (301 mmol) of 2,3-difluoro-1-bromobenzene in 600 ml of THF was added by drops thereto so that the reaction temperature was maintained at about 50° C. and then stirred at room temperature for 1 hour. To the reaction solution was added by drops a solution of 70.0 g (251 mmol) of the crude 4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butanal obtained by the same manner as in the fifth step of Example 1 in 700 ml of THF, stirred at 50 to 60° C. for 2 hours, and then 200 ml of saturated aqueous ammonium chloride solution was added thereto to terminate the reaction. The reaction mixture was filtered with Celite, the solvent was distilled off under a reduced pressure, and then the residue was extracted with 700 ml of toluene. The organic layer was washed with 400 ml of water thrice and then dried over anhydrous magnesium sulfate. After the anhydrous magnesium sulfate was filtered off, 3.56 g of p-toluenesulfonic acid monohydrate was added to the filtrate, and heated to reflux for 4 hours. The organic layer was washed with 300 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 63.5 g of a crude 2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)-1-butenyl)benzene.

Second Step

To 600 ml of mixed solvent of toluene/Solmix (1/1) was dissolved 63.5 g (170 mmol) of the crude product obtained by the procedures described above, 3.18 g of 5% by weight-palladium/carbon catalyst was added thereto, and then they were stirred at room temperature under the condition of a hydrogen gas pressure of 1 to 2 kg/cm² for 6 hours. After the catalyst was removed from the reaction mixture by filtration, the solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 60.0 g of a crude 2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene.

Third Step

Under nitrogen gas stream, 60.0 g (159 mmol) of the crude 2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene was dissolved in 600 ml of THF, cooled down to −70° C., and 191 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature and stirred at the same temperature for 2 hours. To the reaction mixture was added by drops a solution of 60.7 g (239 mmol) of iodine in 600 ml of THF while being maintained at the same temperature, the reaction temperature was gradually raised up to room temperature, and then they were stirred for 30 minutes. The reaction mixture was added to 300 ml of saturated aqueous sodium thiosulfate solution to terminate the reaction, and the solvent was distilled off under a reduced pressure. The residue was extracted with 700 ml of toluene, and the organic layer was washed with 300 ml of saturated aqueous sodium thiosulfate solution twice and 200 ml of saturated aqueous sodium carbonate solution once, and 300 ml of water thrice, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: heptane) to obtain 72.5 g. of a crude 2,3-difluoro-1-iodo-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene.

Fourth Step

Under nitrogen gas stream, a solution prepared by dissolving 9.46 g (59.8 mmol) of 2,3-difluoro-1-ethoxybenzene in 100 ml of THF was cooled down to −70° C., and 59.8 ml of sec-butyl lithium (1.0M, cyclohexane solution) was added by drops thereto while being maintained at the same temperature and stirred at the same temperature for 2 hors. To the reaction mixture was added by drops 120 ml of zinc chloride (0.5M, THF solution), stirred at the same temperature for 1 hour, the reaction temperature was gradually raised up to room temperature, and they were stirred for further 1 hour. To the reaction mixture was added 1.00 g of tetrakis(triphenylphosphine)palladium (0), and a solution of 25.0 g (49.8 mmol) of the crude 2,3-difluoro-1-iodo-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)benzene in 250 ml of THF was added by drops thereto and heated to reflux for 3 hours. The reaction mixture was added to 200 ml of water to terminate the reaction, the solvent was distilled off under a reduced pressure, and the concentrated residue was extracted with 500 ml of toluene. The organic layer was washed with 300 ml of water thrice and dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: mixed solvent of heptane/toluene=7/3) to obtain a crude 1-ethoxy-2,3-difluoro-4-(2,3-difluoro-4-(4-(trans-4-(trans-4-propylcyclohexyl)cyclohexyl)butyl)phenyl)benzene. This crude product was recrystallized from heptane once and from mixed solvent of heptane/ethanol (5/1) once to obtain 13.1 g (yield 28.3%) of the subject compound.

Phase transition temperature: C 89.5 N 193.2 Iso; ¹H-NMR: δ: (ppm): 0.40˜2.10 (m, 36H), 2.70 (t, 2H, J=6.9 Hz), 4.17 (q, 2H, J=7.2 Hz), 6.60˜7.20 (m, 4H); MS: m/e=532 (M⁺).

Following the methods of Example 1 to 5, the following compounds can be prepared:

R¹

m n Y¹ 1 C₃H₇

0 0 C₅H₁₁ 2 C₅H₁₁

0 0 C₇H₁₅ 3 C₇H₁₅

0 0 C₃H₇ 4 C₃H₇

0 0 OC₂H₅ 5 C₅H₁₁O

0 0 OC₄H₉ 6 C₅H₁₁

0 0 OC₂H₅ 7 C₃H₇

0 0 C₃H₇ 8 C₅H₁₁

0 0 C₇H₁₅ 9 C₇H₁₅

0 0 C₅H₁₁ 10

0 0 OC₄H₉ 11 C₅H₁₁

0 0 OC₂H₅ 12 C₇H₁₅

0 0 OCH₃ 13 C₃H₇

0 0 C₇H₁₅ 14 C₅H₁₁

0 0 C₅H₁₁ 15 C₇H₁₅

0 0 C₃H₇ 16 C₃H₇

0 0 OC₂H₅ 17 C₅H₁₁

0 0 OC₄H₉ 18 C₃H₇O

0 0 OC₅H₁₁ 19 C₃H₇

1 0 C₅H₁₁ 20 C₅H₁₁

1 0 C₃H₇ C 40.2 S_(B) 90.9 N 98.0 Iso 21 C₃H₇O

1 0 C₇H₁₅ 22 C₃H₇

1 0 OC₄H₉ 23 C₅H₁₁

1 0 OC₂H₅ C 79.2 S_(A) 94.5 N 125.5 Iso 24 C₇H₁₅

1 0 OCH₃ 25 C₃H₇

1 0 C₇H₁₅ 26 C₅H₁₁

1 0 C₅H₁₁ 27 C₇H₁₅

1 0 C₃H₇ 28 C₃H₇

1 0 OC₄H₉ 29 C₅H₁₁

1 0 OC₂H₅ 30 C₅H₁₁O

1 0 OCH₃ 31 C₃H₇

1 0 C₅H₁₁ 32 C₅H₁₁

1 0 C₃H₇ 33

1 0 CH₃ 34 C₃H₇

1 0 OC₄H₉ 35 C₅H₁₁

1 0 OC₂H₅ 36 C₇H₁₅

1 0 OC₃H₇ 37 C₃H₇

1 0 C₃H₇ 38 C₅H₁₁

1 0 C₅H₁₁ 39 C₂H₅

1 0 C₅H₁₁ 40 C₃H₇

1 0 OC₄H₉ 41 C₅H₁₁

1 0 OC₂H₅ 42 C₆H₁₃O

1 0 OCH₃ 43 C₃H₇

1 0 C₅H₁₁ 44 C₅H₁₁

1 0 C₃H₇ 45 C₂H₅O

1 0 C₇H₁₅ 46 C₃H₇

1 0 OC₂H₅ 47 C₅H₁₁

1 0 OC₄H₉ 48 C₇H₁₅

1 0 OCH₃ 49 C₃H₇

1 0 C₃H₇ 50 C₅H₁₁

1 0 C₅H₁₁ 51

1 0 C₂H₅ 52 C₃H₇

1 0 OC₄H₉ 53 C₅H₁₁

1 0 OC₃H₇ 54 C₇H₁₅

1 0 OC₂H₅ 55 C₅H₁₁

1 0 C₃H₇ 56 C₃H₇

1 0 C₅H₁₁ 57 C₅H₁₁O

1 0 C₃H₇ 58 C₃H₇

1 0 OC₂H₅ 59 C₅H₁₁

1 0 OC₄H₉ 60

1 0 OC₃H₇ 61 C₃H₇

1 0 C₇H₁₅ 62 C₅H₁₁

1 0 C₃H₇ 63 C₇H₁₅

1 0 C₅H₁₁ 64 C₃H₇

1 0 OC₂H₅ 65 C₅H₁₁

1 0 OC₄H₉ 66

1 0 OCH₃ 67 C₃H₇

1 0 C₅H₁₁ 68 C₅H₁₁

1 0 C₃H₇ 69 C₇H₁₅

1 0 C₂H₅ 70 C₃H₇

1 0 OC₂H₉ 71 C₅H₁₁

1 0 OC₃H₇ 72 C₇H₁₅

1 0 OC₄H₉ 73 C₃H₇

1 0 C₃H₇ 74 C₅H₁₁

1 0 C₅H₁₁ 75 C₅H₁₁

1 0 C₃H₇ 76 C₃H₇

1 0 OC₂H₅ 77 C₃H₇

1 0 OC₃H₇ 78 C₇H₁₅

1 0 OC₃H₇ 79 C₃H₇

1 0 C₅H₁₁ 80 C₅H₁₁

1 0 C₃H₇ 81 C₇H₁₅

1 0 C₅H₁₁ 82 C₃H₇

1 0 OC₂H₅ 83 C₅H₁₁

1 0 OC₄H₉ 84

1 0 OC₂H₅ 85 C₃H₇

1 0 C₃H₇ 86 C₅H₁₁

1 0 C₅H₁₁ 87 C₅H₁₁

1 0 C₃H₇ 88 C₃H₇

1 0 OC₂H₅ 89 C₅H₁₁

1 0 OC₄H₉ 90 C₇H₁₅

1 0 OC₂H₅ 91 C₃H₇

1 0 C₃H₇ 92 C₅H₁₁

1 0 C₃H₇ 93

1 0 C₅H₁₁ 94 C₃H₇

1 0 OC₂H₅ C 44.4 S_(A) 107.2 N 129.0 Iso 95 C₅H₁₁

1 0 OC₄H₉ 96 C₅H₁₁

1 0 OC₂H₅ 97 C₃H₇

1 0 C₃H₇ 98 C₅H₁₁O

1 0 C₅H₁₁ 99 C₇H₁₅

1 0 C₇H₁₅ 100 C₃H₇

1 0 OC₄H₉ 101 C₅H₁₁

1 0 OC₂H₅ 102 C₅H₁₁

1 0 OC₃H₇ 103 C₃H₇

1 0 C₅H₁₁ 104 C₅H₁₁

1 0 C₃H₇ 105 C₇H₁₅

1 0 CH₃ 106 C₃H₇

1 0 OC₂H₅ 107 C₅H₁₁

1 0 OC₄H₉ 108 C₂H₅O

1 0 OCH₃ 109 C₃H₇

1 0 C₃H₇ 110 C₅H₁₁

1 0 C₅H₁₁ 111 C₅H₁₁

1 0 C₃H₇ 112 C₃H₇O

1 0 OC₄H₉ 113 C₅H₁₁

1 0 OC₂H₅ 114 C₇H₁₅

1 0 OCH₃ 115 C₃H₇

1 0 C₇H₁₅ 116 C₅H₁₁

1 0 C₃H₇ 117

1 0 C₅H₁₁ 118 C₃H₇

1 0 OC₂H₅ 119 C₅H₁₁O

1 0 OC₄H₉ 120 C₅H₁₁

1 0 OC₃H₇ 121 C₃H₇

1 0 C₅H₁₁ 122 C₅H₁₁

1 0 C₃H₇ 123 C₇H₁₅

1 0 C₂H₅ 124

1 0 OC₂H₅ 125 C₅H₁₁

1 0 OC₄H₉ 126 C₇H₁₅

1 0 OC₃H₇ 127 C₃H₇

1 0 C₄H₉ 128 C₅H₁₁

1 0 C₃H₇ 129 C₅H₁₁O

1 0 C₅H₁₁ 130 C₅H₁₁

1 0 OC₄H₉ 131 C₅H₁₁

1 0 OC₂H₅ 132 C₇H₁₅

1 0 OCH₃ 133 C₃H₇

1 0 C₃H₇ 134 C₅H₁₁

1 0 C₂H₅ 135 C₇H₁₅

1 0 C₅H₁₁ 136 C₃H₇

1 0 OC₂H₅ 137 C₅H₁₁

1 0 OC₄H₉ 138 C₅H₁₁

1 0 OC₃H₇ 139 C₃H₇

1 0 C₅H₁₁ 140

1 0 C₃H₇ 141 C₃H₇O

1 0 C₇H₁₅ 142 C₃H₇

1 0 OC₂H₅ 143 C₅H₁₁

1 0 OC₃H₇ 144 C₇H₁₅

1 0 OC₄H₉ 145 C₃H₇

1 1 C₅H₁₁ 146 C₅H₁₁

1 1 C₃H₇ 147 C₃H₇O

1 1 C₇H₁₅ 148 C₃H₇

1 1 OC₄H₉ 149 C₅H₁₁

1 1 OC₂H₅ 150

1 1 OCH₃ 151 C₃H₇

1 1 C₇H₁₅ 152 C₅H₁₁

1 1 C₅H₁₁ 153 C₇H₁₅

1 1 C₃H₇ 154 C₃H₇

1 1 OC₄H₉ 155 C₅H₁₁

1 1 OC₂H₅ 156 C₇H₁₅

1 1 OCH₃ 157 C₃H₇

1 1 C₂H₅ 158 C₅H₁₁

1 1 C₃H₇ 159 C₅H₁₁O

1 1 C₅H₁₁ 160 C₃H₇

1 1 OC₂H₅ 161 C₅H₁₁

1 1 OC₄H₉ 162 C₇H₁₅

1 1 OC₃H₇ 163 C₃H₇

1 1 C₃H₇ 164 C₅H₁₁

1 1 C₅H₁₁ 165 C₃H₇

1 1 C₇H₁₅ 166

1 1 OCH₃ 167 C₅H₁₁

1 1 OC₂H₅ 168 C₇H₁₅

1 1 OC₃H₇ 169 C₃H₇

1 1 C₇H₁₅ 170 C₅H₁₁

1 1 C₅H₁₁ 171 C₇H₁₅

1 1 C₃H₇ 172 C₃H₇

1 1 OC₄H₉ 173 C₅H₁₁O

1 1 OC₂H₅ 174 C₇H₁₅

1 1 OC₃H₇ 175 C₃H₇O

1 1 C₂H₅ 176 C₅H₁₁

1 1 C₃H₇ 177 C₅H₁₁

1 1 C₅H₁₁ 178 C₃H₇

1 1 OC₂H₅ 179 C₅H₁₁

1 1 OC₃H₇ 180 C₃H₇O

1 1 OC₄H₉ 181 C₃H₇

1 1 C₃H₇ 182 C₅H₁₁

1 1 C₇H₁₅ 183

1 1 C₅H₁₁ 184 C₃H₇O

1 1 OCH₃ 185 C₅H₁₁

1 1 OC₂H₅ 186 C₇H₁₅

1 1 OC₃H₇ 187 C₃H₇

1 1 C₇H₁₅ 188 C₅H₁₁

1 1 C₅H₁₁ 189 C₇H₁₅

1 1 C₃H₇ 190 C₃H₇

1 1 OC₄H₉ 191 C₅H₁₁

1 1 OC₂H₅ 192 C₇H₁₅

1 1 OC₃H₇ 193 C₃H₇

1 1 C₂H₅ 194 C₅H₁₁O

1 1 C₃H₇ 195 C₅H₁₁

1 1 C₅H₁₁ 196 C₃H₇

1 1 OC₂H₅ 197 C₅H₁₁

1 1 OC₃H₇ 198 C₃H₇O

1 1 OC₄H₉ 199 C₃H₇

1 1 C₇H₁₅ 200 C₅H₁₁

1 1 C₃H₇ 201

1 1 C₅H₁₁ 202 C₃H₇

1 1 OC₃H₇ 203 C₅H₁₁

1 1 OC₂H₅ 204 C₇H₁₅

1 1 OC₄H₉ 205 C₃H₇

1 1 C₇H₁₅ 206 C₅H₁₁O

1 1 C₅H₁₁ 207 C₇H₁₅

1 1 C₃H₇ 208 C₃H₇

1 1 OC₂H₅ 209 C₅H₁₁

1 1 OCH₃ 210 C₇H₁₅

1 1 OC₃H₇ 211 C₃H₇

1 1 C₂H₅ 212 C₅H₁₁

1 1 C₃H₇ 213 C₃H₇O

1 1 C₅H₁₁ 214 C₅H₁₁

1 1 OC₂H₅ 215 C₅H₁₁

1 1 OC₄H₉ 216 C₃H₇O

1 1 OC₃H₇ 217 C₃H₇

1 1 C₃H₇ 218 C₅H₁₁

1 1 C₃H₇ 219

1 1 C₅H₁₁ 220 C₅H₁₁

1 1 OC₂H₅ 221 C₅H₁₁

1 1 OC₃H₇ 222 C₅H₁₁

1 1 OC₄H₉ 223 C₃H₇

1 1 C₃H₇ 224 C₅H₁₁O

1 1 C₅H₁₁ 225 C₇H₁₅

1 1 C₇H₁₅ 226 C₃H₇

1 1 OC₄H₉ 227 C₅H₁₁

1 1 OC₂H₅ 228 C₅H₁₁

1 1 OC₃H₇ 229 C₃H₇

1 1 C₅H₁₁ 230 C₅H₁₁O

1 1 C₃H₇ 231 C₇H₁₅

1 1 CH₃ 232 C₃H₇

1 1 OC₂H₅ 233 C₅H₁₁

1 1 OC₄H₉ 234 C₂H₅O

1 1 OCH₃ 235 C₃H₇

1 1 C₃H₇ 236 C₅H₁₁

1 1 C₃H₇ 237 C₃H₇

1 1 C₅H₁₁ 238 C₃H₇

1 1 OC₂H₅ C 89.5 N 193.2 Iso 239 C₅H₁₁

1 1 OC₃H₇ 240

1 1 OC₄H₉ 241 C₃H₇

1 1 C₃H₇ 242 C₅H₁₁O

1 1 C₅H₁₁ 243 C₇H₁₅

1 1 C₇H₁₅ 244 C₃H₇

1 1 OC₃H₇ 245 C₅H₁₁

1 1 OC₂H₅ 246 C₅H₁₁

1 1 OC₄H₉ 247 C₃H₇

1 1 C₅H₁₁ 248 C₅H₁₁O

1 1 CH₃ 249 C₇H₁₅

1 1 C₃H₇ 250 C₃H₇

1 1 OCH₃ 251 C₅H₁₁

1 1 OC₂H₅ 252 C₂H₅O

1 1 OC₄H₉ 253 C₃H₇

1 1 C₃H₇ 254 C₅H₁₁

1 1 CH₃ 255

1 1 C₅H₁₁ 256 C₃H₇

1 1 OC₂H₅ 257 C₅H₁₁

1 1 OC₃H₇ 258 C₅H₁₁

1 1 OC₄H₉ 259 C₃H₇

1 1 C₃H₇ 260 C₅H₁₁

1 1 C₅H₁₁ 261 C₇H₁₅

1 1 C₇H₁₅ 262 C₃H₇

1 1 OC₂H₅ 263 C₅H₁₁

1 1 OC₃H₇ 264 C₅H₁₁O

1 1 OC₄H₉ 265 C₃H₇

1 1 C₅H₁₁ 266 C₅H₁₁O

1 1 C₃H₇ 267 C₇H₁₅

1 1 C₃H₇ 268 C₃H₇O

1 1 OCH₃ 269 C₅H₁₁

1 1 OC₄H₉ 270 C₂H₅

1 1 OC₂H₅ 271 C₂H₅

1 1 C₃H₇ 272 C₅H₁₁

1 1 C₃H₇ 273

1 1 C₇H₁₅ 274 C₃H₇

1 1 OC₂H₅ 275 C₅H₁₁

1 1 OC₃H₇ 276 C₇H₁₅

1 1 OC₄H₉ 277 C₃H₇

1 1 C₃H₇ 278 C₅H₁₁

1 1 C₅H₁₁ 279 C₇H₁₅

1 1 CH₃ 280 C₅H₁₁O

1 1 OC₂H₅ 281 C₅H₁₁

1 1 OC₄H₉ 282 C₃H₇

1 1 OC₃H₇ 283 C₃H₇

1 1 C₅H₁₁ 284 C₅H₁₁O

1 1 C₃H₇ 285 C₅H₁₁

1 1 C₅H₁₁ 286 C₃H₇O

1 1 OC₄H₉ 287 C₃H₇

1 1 OCH₃ 288 C₅H₁₁

1 1 OC₂H₅ 289 C₃H₇

0 0 C₃H₇ 290 C₅H₁₁

0 0 OC₂H₅ 291 C₃H₇O

0 0 OC₃H₇ 292 C₃H₇

0 0 C₃H₇ 293 C₅H₁₁

0 0 OC₂H₅ 294 C₇H₁₅

0 0 OCH₃ 295 C₃H₇

0 0 C₇H₁₅ 296 C₂H₅O

0 0 C₅H₁₁ 297 C₅H₁₁

0 0 OC₄H₉ 298

0 0 OC₄H₉ 299 C₅H₁₁

0 0 C₃H₇ 300 C₅H₁₁O

0 0 OCH₃ 301 C₃H₇

0 0 OC₂H₅ 302 C₅H₁₁

0 0 C₃H₇ 303 C₃H₇

0 0 CH₃ 304 C₃H₇

0 0 C₅H₁₁ 305 C₅H₁₁

0 0 OC₂H₅ 306 C₇H₁₅O

0 0 OC₃H₇ 307 C₃H₇

1 0 C₅H₁₁ 308 C₅H₁₁O

1 0 OC₂H₅ 309 C₃H₇

1 0 C₃H₇ 310

1 0 C₃H₇ 311 C₅H₁₁

1 0 OC₂H₅ 312 C₇H₁₅

1 0 C₃H₇ 313 C₃H₇

1 0 C₇H₁₅ 314 C₂H₅O

1 0 C₅H₁₁ 315 C₅H₁₁

1 0 OC₄H₉ 316 C₃H₇

1 0 OC₂H₅ 317 C₅H₁₁O

1 0 C₃H₇ 318 C₅H₁₁

1 0 OCH₃ 319 C₃H₇

1 0 OC₂H₅ 320 C₅H₁₁

1 0 C₃H₇ 321 C₃H₇

1 0 OC₃H₇ 322 C₄H₉

1 0 C₅H₁₁ 323 C₅H₁₁

1 0 OC₂H₅ 324 C₇H₁₅O

1 0 CH₃ 325 C₅H₁₁

1 0 OC₃H₇ 326 C₃H₇

1 0 OC₂H₅ 327 C₅H₁₁

1 0 C₃H₇ 328 C₃H₇

1 0 C₃H₇ 329 C₃H₇O

1 0 C₇H₁₅ 330 C₇H₁₅

1 0 OCH₃ 331 C₃H₇

1 0 OC₂H₅ 332

1 0 C₅H₁₁ 333 C₅H₁₁

1 0 OCH₃ 334 C₂H₅O

1 0 OC₄H₉ 335 C₅H₁₁

1 0 C₃H₇ 336 C₃H₇

1 0 OC₄H₉ 337 C₅H₁₁

1 0 OC₂H₅ 338 C₅H₁₁

1 0 C₃H₇ 339 C₃H₇

1 0 C₅H₁₁ 340 C₅H₁₁O

1 0 CH₃ 341 C₃H₇

1 0 OC₂H₅ 342 C₇H₁₅O

1 0 OC₃H₇ 343 C₅H₁₁

1 1 C₃H₇ 344 C₂H₅O

1 1 OC₂H₅ 345 C₃H₇

1 1 OC₄H₉ 346

1 1 C₃H₇ 347 C₅H₁₁O

1 1 OC₂H₅ 348 C₇H₁₅

1 1 C₅H₁₁ 349 C₅H₁₁

1 1 C₇H₁₅ 350 C₃H₇

1 1 C₅H₁₁ 351 C₅H₁₁

1 1 C₃H₇ 352 C₃H₇

1 1 OC₂H₅ 353 C₅H₁₁O

1 1 C₃H₇ 354 C₄H₉

1 1 OC₃H₇ 355 C₃H₇

1 1 OC₂H₅ 356 C₅H₁₁

1 1 C₃H₇ 357 C₃H₇

1 1 OCH₃ 358 C₃H₇O

1 1 C₅H₁₁ 359 C₅H₁₁

1 1 OC₂H₅ 360 C₇H₁₅O

1 1 CH₃ 361 C₃H₇

1 0 C₃H₇ 362 C₅H₁₁O

1 0 OC₂H₅ 363 C₃H₇

1 1 C₃H₇ 364

1 1 C₅H₁₁ 365 C₅H₁₁

1 0 OC₂H₅ 366 C₇H₁₅

1 0 C₃H₇ 367 C₃H₇

1 1 OC₂H₅ 368 C₂H₅O

1 1 C₅H₁₁ 369 C₅H₁₁

1 1 OC₂H₅ 370 C₃H₇

1 0 C₇H₁₅ 371 C₅H₁₁O

1 0 C₃H₇ 372 C₅H₁₁

1 1 OCH₃ 373 C₃H₇

1 0 CH₃ 374 C₅H₁₁

1 1 C₃H₇ 375 C₃H₇

1 0 OC₃H₇ 376 C₄H₉

1 1 C₅H₁₁ 377 C₅H₁₁

1 1 OC₂H₅ 378 C₇H₁₅O

1 0 OC₄H₉

As nematic liquid crystal compositions comprising the liquid crystalline compound of the present invention produced by such methods as described above, the following Composition Examples (Use Examples 1 through 34) can be shown. In this connection, compounds in the Composition Examples are designated by abbreviation according to the definition shown in Table 1. Further, when the hydrogen atom of trans-1,4-cyclohexylene in the following partial structure was replaced by deuterium (heavy hydrogen) at positions Q₁, Q₂, and Q₃, it is designated by symbol H [1D, 2D, 3D], and when replaced by deuterium at positions Q₅, Q₆, and Q₇, it is designated by symbol H [5D, 6D, 7D]. In other words, the positions where deuterium substituted are indicated by the numeral in the bracket [ ].

In the Composition Examples (Use Examples), “%” means % by weight unless otherwise specified, and “part” means part by weight of an optically active compound based on 100 parts by weight of liquid crystal composition.

Determination of viscosity (η) was conducted at 20.0° C., and determination of each of optical anisotropy (Δn), dielectric anisotropy (Δε), threshold voltage (Vth), and twist pitch (P) was conducted at 25.0° C.

TABLE 1 R—(A₁)—Z₁— . . . —Z_(n)—(A_(n))—X 1) Left side terminal group R- Symbol CH_(2n+1)— n- C_(n)H_(2n+)O— nO- C_(n)H_(2n+1)OC_(m)H_(2m)— nOm- CH₂═CH— V- CH₂=CHC_(n)H_(2n)— Vn- C_(n)H_(2n+1)CH═CHC_(m)H_(2m—) nVm- C_(n)H_(2n+1)CH═CHC_(m)H_(2m)CH═CHC_(k)H_(2k)— nVmVk- 2) Ring structure —(A₁)—, —(A_(n))— Symbol

B

(B)F

B(2F,3F)

B(F,F)

H

Py

D

Ch 3) Bonding group —Z₁—, —Z_(n)— Symbol —C₂H₄— 2 —C₄H₈— 4 —COO— E —C≡C— T —CH═CH— V —CF₂O— CF2O —OCF₂— OCF2 4) Right side terminal group -X Symbol —F —F —Cl —CL —CN —C —CF₃ —CF3 —OCF₃ —OCF3 —OCF₂H —OCF2H —C_(n)H_(2n+1) -n —OC_(n)H_(2n+1) —On —COOCH₃ -EMe —C_(n)H_(2n)CH═CH₂ -nV —C_(m)H_(2m)CH═CHC_(n)H_(2n+1) -mVn —C_(m)H_(2m)CH═CHC_(n)H_(2n)F -mVnF —CH═CF₂ —VFF —C_(n)H_(2n)CH═CF₂ -nVFF —C≡C—CN -TC 5) Example of designation Example 1 3-H2B(F,F)B(F)—F

Example 2 3-HB(F)TB-2

Example 3 1V2-BEB(F,F)—C

USE EXAMPLE 1

5-H4HB(2F, 3F)-3 (No. 20) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% T_(NI) = 77.0 (° C.) Δε = −1.5

USE EXAMPLE 2

5-H4HB(2F, 3F)-O2 (No. 23) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% T_(NI) = 81.8 (° C.) Δε = −2.1

USE EXAMPLE 3

3-HH4B(2F, 3F)-O2 (No. 94) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% T_(NI) = 81.0 (° C.) Δε = −1.9

USE EXAMPLE 4

3-HH4B(2F, 3F)B(2F, 3F)-O2 (No. 238) 15.0% 3-HEB-O4 23.4% 4-HEB-O2 17.6% 5-HEB-O1 17.6% 3-HEB-O2 14.7% 5-HEB-O2 11.7% T_(NI) = 90.2 (° C.) Δε = −2.3

USE EXAMPLE 5

3-HH4B(2F, 3F)-O2 (No. 94) 10.0% 1V2-BEB(F, F)-C  5.0% 3-HB-C 25.0% 1-BTB-3  5.0% 2-BTB-1 10.0% 3-HH-4  6.0% 3-HHB-1 11.0% 3-HHB-3  4.0% 3-H2BTB-2  4.0% 3-H2BTB-3  4.0% 3-H2BTB-4  4.0% 3-HB(F)TB-2  6.0% 3-HB(F)TB-3  6.0% CM33  0.8 part T_(NI) = 90.3 (° C.) η = 17.8 (mPa · s) Δn = 0.165 Δε = 6.5 V_(th) = 2.18 (V) P = 11.3 μm

USE EXAMPLE 6

5-H4HB(2F, 3F)-3 (No. 20) 7.0% V2-HB-C 12.0% 1V2-HB-C 12.0% 3-HB-C 15.0% 3-H[1D, 2D, 3D]-C 9.0% 3-HB(F)-C 5.0% 2-BTB-1 2.0% 3-HH-4 4.0% 3-HH-VFF 6.0% 2-H[1D, 2D, 3D]HB-C 3.0% 3-HHB-C 6.0% 3-HB(F)TB-2 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 4.0% T_(NI) = 87.3 (° C.) η = 19.9 (mPa · s) Δn = 0.154 Δε = 8.5 V_(th) = 2.05 (V)

USE EXAMPLE 7

5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 15.0% 4O1-BEB(F)-C 13.0% 5O1-BEB(F)-C 13.0% 2-HHB(F)-C 15.0% 3-HHB(F)-C 15.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-HB(F)TB-4 4.0% 3-HHB-1 3.0% 3-HHB-O1 4.0% T_(NI) = 88.4 (° C.) η = 88.0 (mPa · s) Δn = 0.149 Δε = 30.6 V_(th) = 0.90 (V)

USE EXAMPLE 8

3-HH4B(2F, 3F)-O2 (No. 94) 6.0% 5-PyB-F 4.0% 3-PyB(F)-F 4.0% 2-BB-C 5.0% 4-BB-C 4.0% 5-BB-C 5.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 6-PyB-O5 3.0% 6-PyB-O6 3.0% 6-PyB-O7 3.0% 6-PyB-O8 3.0% 3-PyBB-F 6.0% 4-PyBB-F 6.0% 5-PyBB-F 6.0% 3-HHB-3 8.0% 2-H2BTB-2 4.0% 2-H2BTB-3 4.0% 2-H2BTB-4 5.0% 3-H2BTB-2 5.0% 3-H2BTB-3 5.0% 3-H2BTB-4 5.0% T_(NI) = 90.8 ° C.) η = 36.4 (mPa · s) Δn = 0.201 Δε = 6.1 V_(th) = 2.31 (V)

USE EXAMPLE 9

5-H4HB(2F, 3F)-3 (No. 20) 4.0% 3-HH4B(2F, 3F)-O2 (No. 94) 3.0% 3-DB-C 10.0% 4-DB-C 10.0% 2-BEB-C 12.0% 3-BEB-C 4.0% 3-PyB(F)-F 6.0% 3-HEB-O4 8.0% 4-HEB-O2 6.0% 5-HEB-O1 6.0% 3-HEB-O2 5.0% 5-HEB-5 5.0% 4-HEB-5 5.0% 1O-BEB-2 4.0% 3-HHB-1 3.0% 3-HHEBB-C 3.0% 3-HBEBB-C 3.0% 5-HBEBB-C 3.0% T_(NI) = 68.1 (° C.) η = 40.5 (mPa · s) Δn = 0.121 Δε = 11.1 V_(th) = 1.35 (V)

USE EXAMPLE 10

5-H4HB(2F, 3F)-3 (No. 20) 4.0% 5-H4HB(2F, 3F)-O2 (No. 23) 4.0% 3-HH4B(2F, 3F)-O2 (No. 94) 4.0% 3-HH4B(2F, 3F)B(2F, 3F)-O2  (No. 238) 4.0% 3-HB-C 18.0% 7-HB-C 3.0% 1O1-HB-C 10.0% 3-HB(F)-C 10.0% 2-PyB-2 2.0% 3-PyB-2 2.0% 4-PyB-2 2.0% 1O1-HH-3 7.0% 2-BTB-O1 7.0% 3-HHB-1 2.0% 3-HHB-F 2.0% 3-HHB-O1 3.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 2-PyBH-3 4.0% 3-PyBH-3 3.0% 3-PyBB-2 3.0% T_(NI) = 72.1 (° C.) η = 23.2 (mPa · s) Δn = 0.140 Δε = 7.1 V_(th) = 1.90 (V)

USE EXAMPLE 11

5-H4HB(2F, 3F)-3 (No. 20) 10.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 12.0% 5O1-BEB(F)-C 4.0% IV2-BEB(F, F)-C 10.0% 3-HH-EMe 10.0% 3-HB-O2 18.0% 7-HEB-F 2.0% 3-HHEB-F 2.0% 5-HHEB-F 2.0% 3-HBEB-F 4.0% 2O1-HBEB(F)-C 2.0% 3-HB(F)EB(F)-C 2.0% 3-HBEB(F, F)-C 2.0% 3-HHB-F 4.0% 3-HHB-O1 4.0% 3-HHB-3 3.0% 3-HEBEB-F 2.0% 3-HEBEB-1 2.0% T_(NI) = 70.0 (° C.) η = 38.0 (mPa · s) Δn = 0.112 Δε = 23.0 V_(th) = 1.04 (V)

USE EXAMPLE 12

3-HH4B(2F, 3F)-O2 (No. 94) 7.0% 5-BEB(F)-C 5.0% V-HB-C 14.0% 5-PyB-C 6.0% 4-BB-3 10.0% 3-HH-2V 10.0% 5-HH-V 6.0% V-HHB-1 7.0% V2-HHB-1 15.0% 3-HHB-1 5.0% 1V2-HBB-2 10.0% 3-HHEBH-3 5.0% T_(NI) = 90.1 (° C.) η = 17.9 (mPa · s) Δn = 0.115 Δε = 4.8 V_(th) = 2.37 (V)

USE EXAMPLE 13

5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 2O1-BEB(F)-C 5.0% 3O1-BEB(F)-C 12.0% 5O1-BEB(F)-C 4.0% 1V2-BEB(F, F)-C 16.0% 3-HB-O2 10.0% 3-HH-4 3.0% 3-HHB-F 3.0% 3-HHB-O1 2.0% 3-HBEB-F 4.0% 3-HHEB-F 7.0% 5-HHEB-F 7.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HB(F)TB-2 5.0% T_(NI) = 84.7 (° C.) η = 43.2 (mPa · s) Δn = 0.140 Δε = 27.5 V_(th) = 1.06 (V)

USE EXAMPLE 14

3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 3-HH3OB(2F, 3F)B(2F, 3F)-5 (No. 237) 4.0% 2-BEB-C 12.0% 3-BEB-C 4.0% 4-BEB-C 6.0% 3-HB-C 28.0% 3-HEB-O4 12.0% 4-HEB-O2 8.0% 5-HEB-O1 8.0% 3-HEB-O2 6.0% 3-HHB-1 3.0% 3-HHB-O1 4.0% T_(NI) = 65.1 (° C.) η = 29.1 (mPa · s) Δn = 0.116 Δε = 9.2 V_(th) = 1.43 (V)

USE EXAMPLE 15

5-H4HB(2F, 3F)-3 (No. 20) 5.0% 2-BEB-C 10.0% 5-BB-C 12.0% 7-BB-C 7.0% 1-BTB-3 7.0% 2-BTB-1 10.0% 1O-BEB-2 10.0% 1O-BEB-5 12.0% 2-HHB-1 4.0% 3-HHB-F 4.0% 3-HHB-1 7.0% 3-HHB-O1 4.0% 3-HHB-3 8.0% T_(NI) = 63.4 (° C.) η = 21.2 (mPa · s) Δn = 0.160 Δε = 6.2 V_(th) = 1.82 (V)

USE EXAMPLE 16

5-H4HB(2F, 3F)-3 (No. 20) 5.0% 5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 1V2-BEB(F, F)-C 8.0% 3-HB-C 10.0% V2V-HB-C 14.0% V2V-HH-3 14.0% 3-HB-O2 4.0% 3-HHB-1 10.0% 3-HHB-3 5.0% 3-HB(F)TB-2 4.0% 3-HB(F)TB-3 4.0% 3-H2BTB-2 4.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% T_(NI) = 98.1 (° C.) η = 20.8 (mPa · s) Δn = 0.130 Δε = 7.2 V_(th) = 2.18 (V)

USE EXAMPLE 17

5-H4HB(2F, 3F)-O2 (No. 23) 5.0% 3-HH4B(2F, 3F)-O2 (No. 94) 5.0% 5-BTB(F)TB-3 10.0% V2-HB-TC 10.0% 3-HB-TC 10.0% 3-HB-C 10.0% 5-HB-C 7.0% 5-BB-C 3.0% 2-BTB-1 10.0% 2-BTB-O1 5.0% 3-HH-4 5.0% 3-HHB-3 11.0% 3-H2BTB-2 3.0% 3-H2BTB-3 3.0% 3-HB(F)TB-2 3.0% T_(NI) = 92.8 (° C.) η = 16.7 (mPa · s) Δn = 0.203 Δε = 6.3 V_(th) = 2.15 (V)

USE EXAMPLE 18

5-H4HB(2F, 3F)-3 (No. 20) 10.0% 2-HHB(F)-F 17.0% 3-HHB(F)-F 17.0% 5-HHB(F)-F 16.0% 2-H2HB(F)-F 10.0% 3-H2HB(F)-F  5.0% 2-HBB(F)-F  6.0% 3-HBB(F)-F  6.0% 5-HBB(F)-F 13.0% CN  0.3 part T_(NI) = 100.8 (° C.) η = 27.3 (mPa · s) Δn = 0.094 Δε = 4.6 V_(th) = 2.25 (V) p = 81 μm

USE EXAMPLE 19

5-H4HB(2F, 3F)-O2 (No. 23) 6.0% 7-HB(F)-F 5.0% 5-H2B(F)-F 5.0% 3-HB-O2 10.0% 3-HH-4 2.0% 3-HH[5D, 6D, 7D]-4 3.0% 2-HHB(F)-F 10.0% 3-HHB(F)-F 10.0% 5-HH[5D, 6D, 7D]B(F)-F 10.0% 3-H2HB(F)-F 5.0% 2-HBB(F)-F 3.0% 3-HBB(F)-F 3.0% 5-HBB(F)-F 6.0% 2-H2BB(F)-F 5.0% 3-H2BB(F)-F 6.0% 3-HHB-1 2.0% 3-HHB-O1 5.0% 3-HHB-3 4.0% T_(NI) = 83.9 (° C.) η = 19.9 (mPa · s) Δn = 0.091 Δε = 3.0 V_(th) = 2.69 (V)

USE EXAMPLE 20

5-H4HB(2F,3F)—O2 (No. 23) 5.0% 3-HH4B(2F,3F)—O2 (No. 94) 5.0% 7-HB(F,F)—F 3.0% 3-HB—O2 7.0% 2-HHB(F)—F 10.0% 3-HHB(F)—F 10.0% 2-HBB(F)—F 9.0% 3-HBB(F)—F 9.0% 5-HBB(F)—F 16.0% 2-HBB—F 4.0% 3-HBB—F 4.0% 5-HBB—F 3.0% 3-HBB(F,F)—F 5.0% 5-HBB(F,F)—F 10.0% T_(NI) = 85.5 (° C.) η = 27.9 (mPa · s) Δn = 0.116 Δε = 5.4 V_(th) = 2.03 (V)

USE EXAMPLE 21

5-H4HB(2F,3F)—3 (No. 20) 5.5% 5-H4HB(2F,3F)—O2 (No. 23) 5.0% 3-HH4B(2F,3F)—O2 (No. 94) 5.0% 7-HB(F,F)—F 3.0% 3-H2HB(F,F)—F 12.0% 4-H2HB(F,F)—F 10.0% 5-H2HB(F,F)—F 10.0% 3-HHB(F,F)—F 5.0% 4-HHB(F,F)—F 5.0% 3-HH2B(F,F)—F 10.0% 3-HBB(F,F)—F 12.0% 5-HBB(F,F)—F 12.0% 3-HBCF2OB(F,F)—F 6.0% T_(NI) = 72.1 (° C.) η = 29.5 (mPa · s) Δn = 0.087 Δε = 8.1 V_(th) = 1.61 (V)

USE EXAMPLE 22

5-H4HB(2F,3F)—O2 (No. 23) 4.0% 3-HH4B(2F,3F)—O2 (No. 94) 3.0% 3-HH4B(2F,3F)B(2F,3F)—O2 (No. 238) 3.0% 7-HB(F,F)—F 5.0% 3-H2HB(F,F)—F 12.0% 3-HHB(F,F)—F 10.0% 4-HHB(F,F)—F 5.0% 3-HBB(F,F)—F 10.0% 3-HHEB(F,F)—F 10.0% 4-HHEB(F,F)—F 3.0% 5-HHEB(F,F)—F 3.0% 2-HBEB(F,F)—F 3.0% 3-HBEB(F,F)—F 5.0% 5-HBEB(F,F)—F 3.0% 3-HDB(F,F)—F 15.0% 3-HHBB(F,F)—F 6.0% T_(NI) = 77.8 (° C.) η = 37.5 (mPa · s) Δn = 0.087 Δε = 12.4 V_(th) = 1.44 (V)

USE EXAMPLE 23

5-H4HB(2F,3F)—O2 (No. 23) 7.0% 3-HH3OB(2F,3F)B(2F,3F)-5 (No. 237) 3.0% 3-HB—CL 10.0% 5-HB—CL 4.0% 7-HB—CL 4.0% 1O1-HH-5 3.0% 2-HBB(F)—F 8.0% 3-HBB(F)—F 8.0% 5-HBB(F)—F 14.0% 4-HHB—CL 8.0% 3-H2HB(F)—CL 4.0% 3-HBB(F,F)—F 10.0% 5-H2BB(F,F)—F 9.0% 3-HB(F)VB-2 4.0% 3-HB(F)VB-3 4.0% T_(NI) = 91.2 (° C.) η = 24.9 (mPa · s) Δn = 0.125 Δε = 4.3 V_(th) = 2.39 (V)

USE EXAMPLE 24

3-HH4B(2F,3F)—O2 (No. 94) 8.0% 3-HH3OB(2F,3F)B(2F,3F)-5 (No. 237) 4.0% 3-HHB(F,F)—F 9.0% 3-H2HB(F,F)—F 8.0% 4-H2HB(F,F)—F 8.0% 3-HBB(F,F)—F 21.0% 5-HBB(F,)—F 20.0% 3-H2BB(F,F)—F 10.0% 5-HHBB(F,F)—F 3.0% 5-HHEBB—F 2.0% 3-HH2BB(F,F)—F 3.0% 1O1-HBBH-4 4.0% T_(NI) = 95.6 (° C.) η = 39.8 (mPa · s) Δn = 0.116 Δε = 8.4 V_(th) = 1.82 (V)

USE EXAMPLE 25

3-HH4B(2F,3F)—O2 (No. 94) 7.0% 5-HB—F 12.0% 6-HB—F 9.0% 7-HB—F 5.0% 2-HHB—OCF3 7.0% 3-HHB—OCF3 7.0% 4-HHB—OCF3 7.0% 3-HH2B—OCF3 4.0% 5-HH2B—OCF3 4.0% 3-HHB(F,F)—OCF3 5.0% 3-HBB(F)—F 10.0% 5-HBB(F)—F 10.0% 3-HH2B(F)—F 3.0% 3-HB(F)BH-3 3.0% 5-HBBH-3 3.0% 3-HHB(F,F)—OCF2H 4.0% T_(NI) = 85.5 (° C.) η = 18.0 (mPa · s) Δn = 0.094 Δε = 4.1 V_(th) = 2.45 (V)

USE EXAMPLE 26

5-H4HB(2F,3F)-3 (No. 20) 5.0% 5-H4HB(2F,3F)—O2 (No. 23) 5.0% 5-H4HB(F,F)—F 7.0% 5-H4HB—OCF3 5.0% 3-H4HB(F,F)—CF3 8.0% 5-H4HB(F,F)—CF3 10.0% 3-HB—CL 6.0% 5-HB—CL 4.0% 2-H2BB(F)—F 5.0% 3-H2BB(F)—F 10.0% 5-HVHB(F,F)—F 5.0% 3-HHB—OCF3 5.0% 3-H2HB—OCF3 5.0% V—HHB(F)—F 5.0% 3-HHB(F)—F 5.0% 5-HHEB—OCF3 2.0% 3-HBEB(F,F)—F 5.0% 5-HH—V2F 3.0% T_(NI) = 68.2 (° C.) η = 27.6 (mPa · s) Δn = 0.094 Δε = 8.0 V_(th) = 1.78 (V)

USE EXAMPLE 27

5-H4HB(2F,3F)-3 (No. 20) 15.0% 3-HEB—O4 23.0% 4-HEB—O2 18.0% 5-HEB—O1 18.0% 3-HEB—O2 14.0% 5-HEB—O2 12.0% T_(NI) = 77.0 (° C.) Δn = 0.087 Δε = −1.5

USE EXAMPLE 28

5-H4HB(2F,3F)-3 (No. 20) 5.0% 3-HH4B(2F,3F)B(2F,3F)—O2 (No. 238) 15.0% 3-HB—O2 10.0% 3-HB—O4 10.0% 3-HH-4 2.0% 5-HH-2 3.0% 3-HEB—O4 15.0% 4-HEB—O2 12.0% 5-HEB—O1 12.0% 3-HEB—O2 9.0% 5-HEB—O2 7.0% T_(NI) = 81.9 (° C.) Δn = 0.090 Δε = −2.6

USE EXAMPLE 29

3-HH4B(2F,3F)—O2 (No. 94) 15.0% 3-HB—O2 15.0% 3-HB—O4 10.0% 3-HEB—O4 10.0% 4-HEB—O2 7.0% 5-HEB—O1 7.0% 3-HEB—O2 6.0% 5-HEB—O2 5.0% 3-HB(2F,3F)—O2 7.0% 5-HHB(2F,3F)—O2 5.0% 5-HBB(2F,3F)-2 5.0% 5-HBB(2F,3F)—O2 4.0% 5-BB(2F,3F)B-3 4.0% T_(NI) = 77.2 (° C.) Δn = 0.105 Δε = −3.1

USE EXAMPLE 30

5-H4HB(2F,3F)-3 (No. 20) 15.0% 5-H4HB(2F,3F)—O2 (No. 23) 10.0% 3-HH4B(2F,3F)—O2 (No. 94) 15.0% 3-HH4B(2F,3F)B(2F,3F)—O2 (No. 238) 5.0% 3-H4B(2F,3F)—O2 (No. 4) 5.0% 3-HB(2F,3F)—O2 20.0% 5-HHB(2F,3F)—O2 10.0% 5-HHB(2F,3F)-1O1 5.0% 5-HBB(2F,3F)-2 10.0% 5-HBB(2F,3F)-1O1 5.0%

USE EXAMPLE 31

5-H4HB(2F,3F)—O2 (No. 23) 10.0% 3-HH4B(2F,3F)—O2 (No. 94) 10.0% 3-H4B(2F,3F)B(2F,3F)—O3 (No. 77) 10.0% 5-HH4HB(2F,3F)—O2 (No. 220) 5.0% 2-HHB(F)—F 2.0% 3-HHB(F)—F 2.0% 5-HHB(F)—F 2.0% 2-HBB(F)—F 6.0% 3-HBB(F)—F 6.0% 5-HBB(F)—F 10.0% 2-H2BB(F)—F 9.0% 3-H2BB(F)—F 9.0% 3-HBB(F,F)—F 14.0% 1O1-HBBH-4 5.0%

USE EXAMPLE 32

3-H4B(2F,3F)—O2 (No. 4) 7.0% 3-HH3OB(2F,3F)-3 (No. 91) 4.0% 5-HH4HB(2F,3F)—O2 (No. 220) 3.0% 5-HB—CL 12.0% 3-HH-4 3.0% 3-HB—O2 17.0% 3-H2HB(F,F)—F 4.0% 3-HHB(F,F)—F 8.0% 3-HBB(F,F)—F 6.0% 2-HHB(F)—F 5.0% 3-HHB(F)—F 5.0% 5-HHB(F)—F 5.0% 2-H2HB(F)—F 2.0% 3-H2HB(F)—F 1.0% 5-H2HB(F)—F 2.0% 3-HHBB(F,F)—F 4.0% 3-HBCF2OB—OCF3 4.0% 5-HBCF2OB(F,F)—CF3 4.0% 3-HHB—O1 4.0%

USE EXAMPLE 33

3-H4B(2,3F)—O2 (No. 4) 5.0% 3-HH3OB(2F,3F)-3 (No. 91) 8.0% 1V2-BEB(F,F)—C 6.0% 3-HB—C 23.0% 2-BTB-1 10.0% 5-HH—VFF 20.0% 1-BHH—VFF 8.0% 1-BHH-2VFF 3.0% 3-H2BTB-2 5.0% 3-H2BTB-3 4.0% 3-H2BTB-4 4.0% 3-HHB-1 4.0%

USE EXAMPLE 34

5-H3OB(2F,3F)—O2 (No. 6) 5.0% 5-H4HB(2F,3F)—O2 (No. 23) 15.0% 3-H4B(2F,3F)B(2F,3F)—O3 (No. 77) 5.0% 2-HB—C 5.0% 3-HB—C 17.0% 3-HB—O2 5.0% 2-BTB-1 3.0% 3-HHB—F 4.0% 3-HHB—O1 5.0% 3-HHEB—F 4.0% 5-HHEB—F 4.0% 2-HHB(F)—F 7.0% 3-HHB(F)—F 7.0% 5-HHB(F)—F 7.0% 3-HHB(F,F)—F 5.0%

As will be understood from the Examples described above, the compounds of the present invention, that is, any two to four rings compounds having butylene group or propylenoxy group, and 2,3-difluorophenyl group in the skeleton structure at the same time have the following characteristics:

1) The compounds are wide in temperature range of exhibiting a liquid crystal phase, and are extremely high in capability of developing nematic phase.

2) Improvement in response speed in IPS mode is noticed with the compounds, since the compounds have a negative and large Δε.

3) A low viscosity, low threshold voltage, and improvement in response speed are noticed with the compounds.

4) Separation of crystals or development of smectic phase is not observed with the compounds even at very low temperatures, and stabilized nematic liquid crystal compositions can be produced from the compounds.

INDUSTRIAL APPLICABILITY

Compounds of the present invention exhibit the characteristics described in 1) to 4) above, are stable against outside environment, and can provide novel liquid crystal compositions and liquid crystal display devices by which realization of expansion of temperature range of use, driving at a low voltage, and a high speed response is possible. 

What is claimed is:
 1. A liquid crystalline compound expressed by the general formula (1)

wherein R¹ represents an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a fluorine atom; X¹, X², and X³ independently represent —(CH₂)₄—, —(CH₂)₃O—, —O(CH₂)₃—, or single bond, provided that one of X¹, X², and X³ represents —(CH₂)₄—, —(CH₂)₃O—, or —O(CH₂)₃—, and the others represent single bonds; Y¹ represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1, provided that when both m and n are 0, and ring A¹ represents trans-1,4-cyclohexylene group, then X¹ represents —(CH₂)₄—, that when m is 1, n is 0, and both ring A¹ and ring A² represent trans-1,4-cyclohexylene group, then X² represents single bond, and that when m is 0, n is 1, and both ring A¹ and ring A³ represent trans-1,4-cyclohexylene group, then X³ represents single bond; and any atom which constitutes this compound may be replaced by its isotope.
 2. The liquid crystalline compound according to claim 1 wherein ring A¹ and ring A² independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X¹ represents —(CH₂)₄— or —(CH₂)₃O—; X² represents single bond; and m is 1 and n is 0 in the general formula (1).
 3. The liquid crystalline compound according to claim 1 wherein ring A¹ and ring A² independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X² represents —(CH₂)₄— or —(CH₂)₃O—; X¹ represents single bond; and m is 1 and n is 0 in the general formula (1).
 4. The liquid crystalline compound according to claim 1 wherein ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X¹ represent —(CH₂)₄— or —(CH₂)₃O—; either X² and X³ represent single bond; and m is 1 and n is 1 in the general formula (1).
 5. The liquid crystalline compound according to claim 1 wherein ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X² represents —(CH₂)₄— or —(CH₂)₃O—; either X¹ and X³ represent single bond; and m is 1 and n is 1 in the general formula (1).
 6. The liquid crystalline compound according to claim 1 wherein ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X³ represents —(CH₂)₄— or —(CH₂)₃O—; either X¹ and X² represent single bond; and m is 1 and n is 1 in the general formula (1).
 7. The liquid crystalline compound according to claim 1 wherein ring A¹ represents 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by fluorine atom; X¹ represents —(CH₂)₄— or —(CH₂)₃O—; and each of m and n is 0 in the general formula (1).
 8. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4)

wherein R² represents an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring C represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; and each atom which constitutes those compounds may be replaced by its isotope.
 9. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by the general formula (5) or (6)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y³ represents —CN or —C≡C—CN; ring D represents trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring F represents trans-1,4-cyclohexylene group or 1,4-phenylene group; Z³ represents 1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom; a, b, and c are independently 0 or 1; and each atom which constitutes those compounds may be replaced by its isotope.
 10. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, and comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12)

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring K and ring M independently represent trans-1,4-cyclohexylene or 1,4-phenylene; L⁶ and L⁷ independently represent hydrogen atom or fluorine atom, but in no case simultaneously represent L⁶ and L⁷ hydrogen atom; Z⁶ and Z⁷ independently represent —CH₂CH₂—, —COO—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.
 11. A liquid crystal composition comprising at least two components, at least one of which is a liquid crystalline compound expressed by the general formula (1)

wherein R¹ represents an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring A¹, ring A², and ring A³ independently represent trans-1,4-cyclohexylene group, trans-1,4-silacyclohexylene group, pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 1,3-dioxane-2,5-diyl group, tetrahydropyran-2,5-diyl group, 1,3-dithian-2,5-diyl group, or tetrahydrothiopyran-2,5-diyl group, or 1,4-phenylene group in which one or more hydrogen atoms on the six-membered ring may be replaced by a fluorine atom; X¹, X², and X³ independently represent —(CH₂)₄—, —(CH₂)₃O—, —O(CH₂)₃—, or single bond, provided that one of X¹, X², and X³ represents —(CH₂)₄—, —(CH₂)₃O—, or —O(CH₂)₃—, and the others represent single bonds; Y¹ represents hydrogen atom or an alkyl group having 1 to 15 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; m and n are independently 0 or 1, provided that when both m and n are 0, and ring A¹ represents trans-1,4-cyclohexylene group, then X¹ represents —(CH₂)₄—, that when m is 1, n is 0, and both ring A¹ and ring A² represent trans-1,4-cyclohexylene group, then X² represents single bond, and that when m is 0, n is 1, and both ring A¹ and ring A³ represent trans-1,4-cyclohexylene group, then X³ represents single bond; and any atom which constitutes this compound may be replaced by its isotope.
 12. A liquid crystal composition comprising at least one optically active compound in addition to the liquid crystal composition defined in claim
 11. 13. A liquid crystal display device fabricated by using the liquid crystal composition defined in claim
 11. 14. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R² represents an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring C represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; and each atom which constitutes those compounds may be replaced by its isotope,

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one hydrogen atom may be replaced by fluorine atom; Z⁴ and Z⁵ independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡C—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.
 15. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (10), (11), and (12)

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one hydrogen atom may be replaced by fluorine atom; Z⁴ and Z⁵ independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡C—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope,

wherein R⁷ and R⁸ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring K and ring M independently represent trans-1,4-cyclohexylene or 1,4-phenylene; L⁶ and L⁷ independently represent hydrogen atom or fluorine atom, but in no case simultaneously represent L⁶ and L⁷ hydrogen atom; Z⁶ and Z⁷ independently represent —CH₂CH₂—, —COO—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.
 16. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R² represents an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring C represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; and each atom which constitutes those compounds may be replaced by its isotope,

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one hydrogen atom may be replaced by fluorine atom; Z⁴ and Z⁵ independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡C—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.
 17. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formula (5) or (6), and comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y³ represents —CN or —C≡C—CN; ring D represents trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring F represents trans-1,4-cyclohexylene group or 1,4-phenylene group; Z³ represents 1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom; a, b, and c are independently 0 or 1; and each atom which constitutes those compounds may be replaced by its isotope,

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one hydrogen atom may be replaced by fluorine atom; Z⁴ and Z⁵ independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡C—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope.
 18. A liquid crystal composition comprising, as a first component, at least one liquid crystalline compound defined in any one of claims 1-7, comprising, as a second component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (2), (3), and (4), comprising, as a third component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formula (5) or (6), and comprising, as a fourth component, at least one compound selected from the group consisting of the compounds expressed by any one of the general formulas (7), (8), and (9)

wherein R² represents an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group; and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y² represents fluorine atom, chlorine atom, —OCF₃, —OCF₂H, —CF₃, —CF₂H, —CFH₂, —OCF₂CF₂H, or —OCF₂CFHCF₃; L¹ and L² independently represent hydrogen atom or fluorine atom; Z¹ and Z² independently represent 1,2-ethylene group, vinylene group, 1,4-butylene group, —COO—, —CF₂O—, —OCF₂—, or single bond; ring B represents trans-1,4-cyclohexylene group or 1,3-dioxane-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring C represents trans-1,4-cyclohexylene group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; and each atom which constitutes those compounds may be replaced by its isotope,

wherein R³ and R⁴ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; Y³ represents —CN or —C≡C—CN; ring D represents trans-1,4-cyclohexylene group, 1,4-phenylene group, pyrimidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group; ring E represents trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which hydrogen atom may be replaced by fluorine atom; ring F represents trans-1,4-cyclohexylene group or 1,4-phenylene group; Z³ represents 1,2-ethylene group, —COO—, or single bond; L³, L⁴, and L⁵ independently represent hydrogen atom or fluorine atom; a, b, and c are independently 0 or 1; and each atom which constitutes those compounds may be replaced by its isotope,

wherein R⁵ and R⁶ independently represent an alkyl group having 1 to 10 carbon atoms in which alkyl group not-adjacent any methylene group may be replaced by oxygen atom or vinylene group, and any hydrogen atom in the alkyl group may be replaced by fluorine atom; ring G, ring I, and ring J independently represent trans-1,4-cyclohexylene group or pyrimidine-2,5-diyl group, or 1,4-phenylene group in which one hydrogen atom may be replaced by fluorine atom; Z⁴ and Z⁵ independently represent 1,2-ethylene group, vinylene group, —COO—, —C≡C—, or single bond; and each atom which constitutes those compounds may be replaced by its isotope. 